Method for manufacture of zeolite beta in the presence of ODSO

ABSTRACT

The present disclosure is directed to a method of manufacture of beta zeolites. This is accomplished by using an improved sol-gel formulation including a water-soluble fraction of ODSO as an additional component. The resulting products are, or contain, beta zeolites, with increased yield.

FIELD OF THE DISCLOSURE

The present disclosure relates to methods of making zeolites.

BACKGROUND OF THE DISCLOSURE

Zeolites (*BEA)

Zeolites are crystalline solids possessing well-defined structures anduniform pore sizes that can be measured in angstroms (Å). Typically,zeolites comprise framework atoms such as silicon, aluminum and oxygenarranged as silica and alumina tetrahedra. Zeolites are generallyhydrated aluminum silicates that can be made or selected with acontrolled porosity and other characteristics, and typically containcations, water and/or other molecules located in the porous network.Hundreds of natural and synthetic zeolite framework types exist with awide range of applications. Numerous zeolites occur naturally and areextensively mined, whereas a wealth of interdependent research hasresulted in an abundance of synthetic zeolites of different structuresand compositions. The unique properties of zeolites and the ability totailor zeolites for specific applications has resulted in the extensiveuse of zeolites in industry as catalysts, molecular sieves, adsorbents,ion exchange materials and for the separation of gases. Certain types ofzeolites find application in various processes in petroleum refineriesand many other applications. The zeolite pores can form sites forcatalytic reactions, and can also form channels that are selective forthe passage of certain compounds and/or isomers to the exclusion ofothers.

Zeolites can also possess an acidity level that enhances its efficacy asa catalytic material or adsorbent, alone or with the addition of activecomponents. In particular, highly acidic zeolites in thehydrogen-exchanged form are useful, including zeolite beta (*BEA) (where*BEA is the code established by the International Zeolite Association).

Zeolite beta contains the *BEA framework, which includes zeolite betapolymorph A, having a micropore size related to the 12-member rings whenviewed along the [100] and [001] directions of 6.6×6.7 Å and 5.6×5.6 Å,respectively.

Numerous methods have been reported for the synthesis of zeolite beta.An example of the synthesis of zeolite beta uses the tetraethylammoniumion as a structure directing agent.

ODSO

Within a typical refinery, there are by-product streams that must betreated or otherwise disposed of. The mercaptan oxidation process,commonly referred to as the MEROX process, has long been employed forthe removal of the generally foul smelling mercaptans found in manyhydrocarbon streams and was introduced in the refining industry overfifty years ago. Because of regulatory requirements for the reduction ofthe sulfur content of fuels for environmental reasons, refineries havebeen, and continue to be faced with the disposal of large volumes ofsulfur-containing by-products. Disulfide oil (DSO) compounds areproduced as a by-product of the MEROX process in which the mercaptansare removed from any of a variety of petroleum streams includingliquefied petroleum gas, naphtha, and other hydrocarbon fractions. It iscommonly referred to as a ‘sweetening process’ because it removes thesour or foul smelling mercaptans present in crude petroleum. The term“DSO” is used for convenience in this description and in the claims, andwill be understood to include the mixture of disulfide oils produced asby-products of the mercaptan oxidation process. Examples of DSO includedimethyldisulfide, diethyldisulfide, and methylethyldisulfide.

The by-product DSO compounds produced by the MEROX unit can be processedand/or disposed of during the operation of various other refinery units.For example, DSO can be added to the fuel oil pool at the expense of aresulting higher sulfur content of the pool. DSO can be processed in ahydrotreating/hydrocracking unit at the expense of higher hydrogenconsumption. DSO also has an unpleasant foul or sour smell, which issomewhat less prevalent because of its relatively lower vapor pressureat ambient temperature; however, problems exist in the handling of thisoil.

Commonly owned U.S. Pat. No. 10,807,947 which is incorporated byreference herein in its entirety discloses a controlled catalyticoxidation of MEROX process by-products DSO. The resulting oxidizedmaterial is referred to as oxidized disulfide oil (ODSO). As disclosedin 10,807,947, the by-product DSO compounds from the mercaptan oxidationprocess can be oxidized, in the presence of a catalyst. The oxidationreaction products constitute an abundant source of ODSO compounds,sulfoxides, sulfonates, sulfinates and sulfones.

The ODSO stream co-produced contains ODSO compounds as disclosed in U.S.Pat. Nos. 10,781,168 and 11,111,212 as compositions (such as a solvent),in U.S. Pat. No. 10,793,782 as an aromatics extraction solvent, and inU.S. Pat. No. 10,927,318 as a lubricity additive, all of which areincorporated by reference herein in their entireties. In the event thata refiner has produced or has on hand an amount of DSO compounds that isin excess of foreseeable needs for these or other uses, the refiner maywish to dispose of the DSO compounds in order to clear a storage vesseland/or eliminate the product from inventory for tax reasons.

Thus, there is a clear and long-standing need to provide an efficientand economical process for the treatment of the large volumes of DSOby-products and their derivatives to effect and modify their propertiesin order to facilitate and simplify their environmentally acceptabledisposal, and to utilize the modified products in an economically andenvironmentally friendly manner, and thereby enhance the value of thisclass of by-products to the refiner.

Despite the known ways to produce *BEA zeolites, there remains a need inthe art for improved methods to produce zeolite materials, in particularusing DSO by-products in an economically and environmentally friendlymanner. It is in regard to these and other problems in the art that thepresent disclosure is directed to provide a technical solution for aneffective method of manufacturing *BEA zeolites.

SUMMARY OF THE DISCLOSURE

A method for the preparation of beta zeolite is provided. The methodcomprises: forming a homogeneous aqueous mixture of water, a silicasource, an aluminum source, an alkali metal source, an optionalstructure directing agent, and an effective amount of water-solubleoxidized disulfide oil (ODSO); and heating the homogeneous aqueousmixture under conditions and for a time effective for hydrolysis and toform a crystalline zeolite as precipitate suspended in a supernatant,wherein the precipitate contains beta zeolite. In certain embodiments,the precipitate is recovered and calcined at a suitable temperature,temperature ramp rate and for a suitable period of time to realizeporous beta zeolite.

In certain embodiments, a cumulative amount of ODSO and water isapproximately equivalent to an amount of water that is effective toproduce beta zeolite in the absence of ODSO; the cumulative amount ofODSO and water, an amount of the silica source, an amount of thealuminum source, an amount of the alkali metal source, and an amount ofthe optional structure directing agent are provided at an ODSO-enhancedcompositional ratio; the ODSO-enhanced compositional ratio isapproximately equivalent to a baseline compositional ratio of water,silica source, aluminum source, alkali metal source and optionalstructure directing agent, the baseline compositional ratio beingeffective to produce beta zeolite in the absence of ODSO; and theconditions and time of heating are approximately equivalent to thosethat are effective to produce beta zeolite in the absence of ODSO. Incertain embodiments, the effective amount of ODSO is greater than 0.1mass % ODSO relative to the total mass of the homogeneous aqueousmixture, and is less than an amount of ODSO that produces only zeolitemordenite. In certain embodiments, the effective amount of ODSO isgreater than an amount of ODSO that produces only zeolite mordenite, andless than an amount of ODSO that produces only amorphous material and/orother crystalline material. In certain embodiments, the alkali metalsource is sodium and the mass ratio of ODSO to sodium is in the range ofabout 0.1 to 1.8 or 7.5-8.5.

In certain embodiments, the ODSO is derived from oxidation of disulfideoil compounds present in an effluent refinery hydrocarbon streamrecovered following catalytic oxidation of mercaptans present in amercaptan-containing hydrocarbon stream. In certain embodiments, theODSO compounds have 3 or more oxygen atoms and include one or morecompounds selected from the group consisting of (R—SOO—SO—R′),(R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH),(R—SO—SO—OR′), (R—SOO—SO—OR′), (R—SO—SOO—OR′) and (R—SOO—SOO—OR′),wherein R and R′ can be the same or different C1-C10 alkyl or C6-C10aryl. In certain embodiments, the ODSO compounds have 3 or more oxygenatoms and include two or more compounds selected from the groupconsisting of (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH),(R—SOO—SOO—OH), (R—SOO—SO—OH), (R—SO—SO—OR′), (R—SOO—SO—OR′),(R—SO—SOO—OR′) and (R—SOO—SOO—OR′), wherein R and R′ can be the same ordifferent C1-C10 alkyl or C6-C10 aryl. In certain embodiments, the ODSOcompounds have 3 or more oxygen atoms and include one or more compoundsselected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), wherein Rand R′ can be the same or different C1-C10 alkyl or C6-C10 aryl. Incertain embodiments, the silica-to-alumina ratio (SAR) in the zeoliteproduct is between about 10 and 10000.

Any combinations of the various embodiments and implementationsdisclosed herein can be used. These and other aspects and features canbe appreciated from the following description of certain embodiments andthe accompanying drawings and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a simplified schematic diagram of a generalized version of aconventional mercaptan oxidation or MEROX process for the liquid-liquidextraction of a mercaptan containing hydrocarbon stream.

FIG. 2 is a simplified schematic diagram of a generalized version of anenhanced mercaptan oxidation or E-MEROX process.

FIG. 3A is the experimental 1H-NMR spectrum of the polar, water-solubleODSO fraction used in an example herein.

FIG. 3B is the experimental ¹³C-DEPT-135-NMR spectrum of the polar,water-soluble ODSO fraction used in an example herein.

FIG. 4 shows X-ray diffraction patterns of the beta zeolite synthesizedusing ODSO as in an example herein compared with beta zeolitesynthesized in the absence of ODSO as in a comparative example herein.

FIG. 5 is a plot of thermogravimetric (TGA) and derivativethermogravimetric (DTG) mass loss profiles of the beta zeolitesynthesized in the presence of ODSO and water as in an example hereincompared with beta zeolite synthesized in the absence of ODSO as in acomparative example herein.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE DISCLOSURE

The present disclosure is directed to a method of manufacture of *BEAzeolites. This is accomplished by using an improved sol-gel formulationincluding a water-soluble fraction of ODSO as an additional component.The resulting products are, or contain, *BEA zeolites at increasedyields relative to synthesis in the absence of ODSO.

In conventional beta zeolite synthesis, water is used as an aqueousmedium and as a solvent. In the embodiments of the present disclosure,an effective amount of water-soluble ODSO compounds is added as anadditional component within a homogeneous aqueous mixture. In certainembodiments, the ODSO is derived from a sulfur-containing refinery wastestream and is used as an additional component for the synthesis of betazeolite.

In certain embodiments, when compared with an equivalent water-onlysynthesis that is conventional in the sol-gel synthesis of zeolite beta,the inclusion of an effective amount of ODSO to the homogeneous aqueousmixture results an increase in the overall zeolite yield compared withan equivalent water-only synthesis for beta zeolite. For example,compared with an equivalent water-only synthesis for beta zeolite, theuse of the ODSO compounds in the syntheses herein increases the overallzeolite yield by about 1-100, 1-75, 10-100, 10-75, 1-20, 1-15, 1-10,5-20 or 5-15 mass %.

In certain embodiments the zeolites formed herein, the content ofzeolite beta is in the range of about 0.1-100, 1-100, 5-100, 10-100,25-100, 50-100, 75-100 or 90-100 mass % (wherein the mass % of zeolitebeta to the combined product mass of zeolite beta and any otheramorphous or crystalline products that are formed). The remainder (ifthe product is not 100% zeolite beta) can be zeolite mordenite,amorphous materials, or other unidentified crystalline materials. Incertain embodiments the synthesized zeolite beta has a crystal latticeconstant of a=1.26 nm to 1.27 nm, b=1.26 nm to 1.27 nm and c=2.62 nm to2.65 nm.

Synthesis Steps

Methods for the preparation of beta zeolites are provided. Effectiveamounts of precursors and reagents are formed as a homogeneous aqueousmixture, including a water source, an aluminum source, a silica source,an alkali metal source, and an optional structure directing agent. Inthe place of a certain amount of water, an effective amount ofwater-soluble ODSO is used as an additional component. The componentsare mixed for an effective time and under conditions suitable to formthe homogeneous aqueous mixture. The chronological sequence of mixingcan vary, with the objective being a highly homogenous distribution ofthe components in an aqueous mixture. The homogeneous aqueous mixture isheated under conditions and for a time effective to form a precipitate(product) suspended in a supernatant (mother liquor). The precipitate isrecovered, for example by filtration, washing and drying, as betazeolites. In certain embodiments the recovered product is calcined at asuitable temperature, temperature ramp rate and for a suitable period oftime to realize porous beta zeolite.

An effective amount of water for the aqueous environment and as asolvent during the sol-gel process can be provided from one or morewater sources, including utility water that is added to form thehomogeneous aqueous mixture, a water-containing silica source such ascolloidal silica, an aqueous mixture of an aluminum oxide source, anaqueous mixture of an alkali metal source and/or an aqueous mixture ofan optional structure directing agent. The mixture components are addedwith water to the reaction vessel prior to heating. Typically, waterallows for adequate mixing to realize a more homogeneous distribution ofthe sol-gel components, which ultimately produces a more desirableproduct because each crystal is more closely matched in properties tothe next crystal. Insufficient mixing could result in undesirable“pockets” of highly concentrated sol-gel components and this may lead toimpurities in the form of different structural phases or morphologies.Water also determines the yield per volume. In the descriptions thatfollow, it is understood that water is a component of homogeneousaqueous mixtures from one or more of the sources of water.

In certain embodiments, a homogeneous aqueous mixture is formed by:providing a silica source; combining an aluminum oxide source, an alkalimetal source and an optional structure directing agent; and combining aneffective amount of water-soluble ODSO. Alternatively, the water-solubleODSO is combined with the aluminum oxide source, the alkali metal sourceand the optional structure directing agent, and that mixture is combinedwith the silica source.

In certain embodiments, a homogeneous aqueous mixture is formed by:providing an aluminum oxide source, an alkali metal source and anoptional structure directing agent as a mixture; combining a silicasource; and combining an effective amount of water-soluble ODSO.Alternatively, the water-soluble ODSO is combined with the silicasource, and that mixture is combined with the aluminum oxide source, thealkali metal source and the optional structure directing agent.

In certain embodiments, a homogeneous aqueous mixture is formed by:forming an aqueous solution of an aluminum source, an alkali metalsource and an optional structure directing agent; adding to the aqueoussolution an effective amount of water-soluble ODSO; adding a silicasource, since addition of the silica source forms a thick gel. In otherembodiments, all or a portion of an effective amount of water-solubleODSO can be added to the silica source, and that mixture is added to anaqueous solution of an aluminum source, an alkali metal source and anoptional structure directing agent.

In certain embodiments, a homogeneous aqueous mixture is formed by:combining an effective amount of water-soluble ODSO with a silica sourceto form a mixture; and that mixture is combined with an aluminum oxidesource, an alkali metal source and an optional structure directingagent.

In certain embodiments, a homogeneous aqueous mixture is formed by:combining an effective amount of water-soluble ODSO with an aluminumoxide source, an alkali metal source and an optional structure directingagent to form a mixture; and that mixture is combined with a silicasource.

A homogeneous aqueous mixture of an aluminum source, a silica source, analkali metal source, water-soluble ODSO and an optional structuredirecting agent is formed from any of the above chronological sequencesof component addition. The homogeneous aqueous mixture is heated underconditions and for a time effective to form a precipitate suspended in asupernatant, wherein the time and conditions are effective to realizethe precipitate containing beta zeolite, which is recovered, for exampleby filtration, washing and drying. In certain embodiments the recoveredprecipitate is calcined at a suitable temperature, temperature ramp rateand for a suitable period of time to realize porous beta zeolite.

It is to be appreciated by those skilled in the art that in certainembodiments effective baseline compositional ratios for synthesis ofzeolites including beta zeolite can be determined by empirical data, forinstance summarized as phase boundary diagrams or other methodologies asis known in material synthesis. It is also to be realized that accordingto certain embodiments of the process herein, inclusion of an ODSOcomponent results in shifting the material type out of the phaseboundary diagram even at approximately equivalent baseline compositionalratios. For instance, with certain baseline ratios for synthesis of betazeolite, increasing amounts of ODSO added to the sol-gel system resultsin mordenite zeolite; a further increase results in co-crystallized betazeolite and mordenite zeolite.

In certain embodiments, effective ratios of precursors and reagents forproduction of zeolites herein are within those known to producetemplated aluminosilicate zeolites and can be determined by those ofordinary skill in the art. For example, effective amounts of silica andalumina precursors are provided to produce synthesized zeolite having asilica-to-alumina ratio (SAR) in the range of about 10-10000, 10-5000,10-500, 10-100, 10-80, 50-10000, 50-5000, 50-1000, 50-500 or 50-100. Incertain embodiments, baseline compositional ratios of the aqueouscomposition used produce zeolites herein include (on a molar basis):

-   -   SiO₂/Al₂O₃: 10-100    -   OH⁻/SiO₂: 0.05-1    -   R/SiO₂: 0-1.0    -   Alkali metal cation/SiO₂: 0.075-1.0    -   H₂O/SiO₂: 5-80    -   wherein R is the structure directing agent, and a level of 0        represents absence of the structure directing agent.        It is appreciated by those skilled in the art that these molar        composition ratios can be expressed on a mass basis. In certain        embodiments, an exemplary compositional ratio is approximately        30 SiO₂:1 Al₂O₃:5.5 Na₂O:15 TEA:750 H₂O on a molar basis.

In the embodiments herein, ratios of components in homogeneous aqueousmixtures including ODSO are referred to as “ODSO-enhanced compositionalratios.” In certain embodiments an ODSO-enhanced compositional ratio isone in which ODSO is included to replace an approximately equivalentmass of water in the homogeneous aqueous mixture, and wherein acumulative mass of ODSO and water (ODSO+H₂O) is approximately equivalentto a mass of water that is effective to produce *BEA zeolites in theabsence of ODSO. In certain embodiments: a baseline compositional ratioof the silica, aluminum, alkali metal, optional structure directingagent and water is known or determined to be is effective to produce*BEA zeolite in the absence of ODSO; an ODSO-enhanced compositionalratio is approximately equivalent to the baseline compositional ratioexcept for the substitution of ODSO for water on a mass basis; andwherein the conditions and time of heating the ODSO-enhanced sol-gel isapproximately equivalent to those that are effective to produce *BEAzeolite in the absence of ODSO.

The aluminum source can comprise, without limitation, one or more ofaluminates, alumina, other zeolites, aluminum colloids, boehmites,pseudo-boehmites, aluminum salts such as aluminum nitrate, aluminumsulfate and alumina chloride, aluminum hydroxides, aluminum alkoxides,aluminum wire and alumina gels. For example, suitable materials asaluminum sources include aluminum nitrate nonahydrate or othercommercially available materials including for instance high purityaluminas (CERALOX commercially available from Sasol) and aluminahydrates (PURAL and CAPITAL commercially available from Sasol),boehmites (DISPERSAL and DISPAL commercially available from Sasol), andsilica-alumina hydrates (SIRAL commercially available from Sasol) andthe corresponding oxides (SIRALOX commercially available from Sasol).

The silica source can comprise, without limitation, one or more ofsilicates including sodium silicate (water glass), rice husk, fumedsilica, precipitated silica, colloidal silica, silica gels, otherzeolites, dealuminated zeolites, and silicon hydroxides and alkoxides.Silica sources resulting in a high relative yield are preferred. Forinstance, suitable materials as silica sources include fumed silicacommercially available from Cabot, and colloidal silica (LUDOXcommercially available from Cabot).

Effective structure directing agents that can optionally be addedinclude known or developed structure directing agents for producingzeolite beta and/or zeolite mordenite. In certain embodiments, effectivestructure directing agents include one or more of quaternary ammoniumions, trialkylamines, dialkylamines, monoalkylamines, cyclic amines,alkylethanol amines, cyclic diamines, alkyl diamines, alkyl polyamines,and other templates including alcohols, ketones, morpholine andglycerol.

In certain embodiments, effective structure directing agents include anyof the thousands of structure directing agents for producing zeolitebeta can be used, as disclosed in Daeyaert, Frits, Fengdan Ye andMichael W. Deem. “Machine-learning approach to the design of OSDAs forzeolite beta.” Proceedings of the National Academy of Sciences of theUnited States of America 116 (2019): 3413-18, which is incorporated byreference herein; in particular those that are computed to stabilize thestructure of beta zeolite can be selected.

In certain embodiments, structure directing agents for producing zeolitebeta include one or more of quaternary ammonium cation compounds,including one or more of tetramethylammonium (TMA) cation compounds,tetraethylammonium (TEA) cation compounds, tetrapropylammonium (TPA)cation compounds, tetrabutylammonium (TBA) cation compounds,cetyltrimethylammonium (CTA) cation compounds. The cation can be pairedwith one or more of a hydroxide anion (for example, TPAOH or CTAOH), abromide anion (for example, TPAB or CTAB), or an iodide anion.

In certain embodiments, other known structure directing agents forproducing zeolite beta can be selected, including but are not limited toone or more of: 4,4′trimethylene bis(N-methyl N-benzyl-piperidinium)hydroxide; 1,2-diazabicyclo 2,2,2, octane (DABCO); dialkylbenzylammonium hydroxide; dimethyldiisopropylammonium hydroxide (DMDPOH);N,N-dimethyl-2,6-cis-dimethylpiperdinium hydroxide (DMPOH);N-ethyl-N,N-dimethylcyclohexanaminium hydroxide (EDMCHOH);N,N,N-trimethylcyclohexanaminium hydroxide (TMCHOH);N-isopropyl-N-methyl-pyrrolidinium (iProOH);N-isobutyl-N-methyl-pyrrolidinium (iButOH); orN-isopentyl-N-methyl-pyrrolidinium (iPenOH).

In the disclosed process for synthesizing beta zeolites, crystallizationcan occur in the absence or presence of seed materials comprisingzeolite structures such as *BEA zeolites. Functions of the seeds caninclude, but are not limited to: supporting growth on the surface of theseed, that is, where crystallization does not undergo nucleation butrather crystal growth is directly on the surface of the seed; the parentgel and seed share common larger composite building units; the parentgel and seed share common smaller units, for instance 4 member rings;seeds that undergo partial dissolution to provide a surface for crystalgrowth of a zeolite; crystallization occurs through a “core-shell”mechanism with the seed acting as a core and the target material growson the surface; and/or where the seeds partially dissolve providingessential building units that can orientate zeolite crystallization.

A hydroxide mineralizer is included as the hydroxide derived from thealkali metal source from the Periodic Table IUPAC Group 1 alkalinemetals (and/or from the hydroxide of any hydroxide-containing structuredirecting agent). For example these are selected from the groupconsisting of NaOH, KOH, RbOH, LiOH, CsOH and combinations thereof. Incertain embodiments a Na-based hydroxide mineralizer is selected. Notethat the alkali metal source is provide as a hydroxide, but inembodiments herein where the ratio is expressed based on the mass of thealkali, it is the metal itself. For instance, when the alkali is NaOH,the ODSO/Na ratio is determined by dividing the mass of the ODSO by themass of the Na portion of NaOH, that is, about 57.5% of the NaOH mass.In certain embodiments the basic components from the hydroxidemineralizer source are provided in effective amounts so as to maintainthe homogeneous mixture at a pH level of greater than or equal to about9, for example in the range of about 9-14, 9-13, 10-14, 10-13, 11-14 or11-13. It is appreciated that the overall pH is influenced by anionsfrom the hydroxide mineralizer source, and in certain embodiments anionsfrom other sources such as from an optional structure directing agent,an alumina source or a silica source. In certain embodiments hydroxideanions are provided as the mineralizer from an alkali metal source and astructure directing agent. In the process herein, the pH is reduced bythe presence of ODSO, therefore, the quantity of the basic compound fromone or more of the aforementioned sources can be adjusted accordingly toattain the requisite pH.

The mixing steps typically occur at ambient temperature and pressure(for instance about 20° C. and about 1 standard atmosphere), for amixing time that sufficient to realize a homogeneous aqueousdistribution of the components. In certain embodiments the homogeneousaqueous mixture can be aged before being subjected to subsequenthydrothermal treatment, for example for a period of about 0-24, 0-5,0.5-24 or 0.5-5 hours. Hydrothermal treatment is carried out at atemperature in the range of about 70-180, 100-180, 120-180, 70-160,100-160, 120-160 or 130-150° C., at atmospheric or autogenous pressure(from the sol-gel or from the sol-gel plus an addition of a gas purgeinto the vessel prior to heating), and for a time period within therange of about 0.1-8, 0.2-8, 0.1-7, 0.2-7, 0,1-6, 0.2-6, 0.1-5 or 0.2-5days, to ensure crystallization and formation of a zeolite gel.

The products are washed, for example with water at a suitable quantity,for example at about twice the volume of the homogeneous aqueousmixture. The wash can be at a temperature of from about 20-80° C.atmospheric, vacuum or under pressure. The wash can continue until thepH of the filtrate approaches about 7-9. The solids are recovered byfiltration, for instance, using known techniques such as centrifugation,gravity, vacuum filtration, filter press, or rotary drums, and dried,for example at a temperature of up to about 110 or 150° C.

The conditions for calcination to produce zeolites herein can includetemperatures in the range of about 450-700, 450-600, 500-700 or 500-600°C., atmospheric pressure, and a time period of about 3-24, 3-18, 6-24 or6-18 hours. Calcining can occur with ramp rates in the range of fromabout 0.1-10, 0.1-5, 0.1-3, 1-10, 1-5 or 1-3° C. per minute. In certainembodiments calcination can have a first step ramping to a temperatureof between about 100-150° C. with a holding time of from about 2-24hours (at ramp rates of from about 0.1-5, 0.1-3, 1-5 or 1-3° C. per min)before increasing to a higher temperature with a final holding time inthe range of about 2-24 hours.

ODSO

Example embodiments of the present disclosure include the use of one ormore ODSO compounds as additional components in a homogeneous aqueousmixture for zeolite synthesis. The additional components can be amixture that comprises two or more ODSO compounds. In the descriptionherein, the terms “oxidized disulfide oil”, “ODSO”, “ODSO mixture” and“ODSO compound(s)” may be used interchangeably for convenience. As usedherein, the abbreviations of oxidized disulfide oils (“ODSO”) anddisulfide oils (“DSO”) will be understood to refer to the singular andplural forms, which may also appear as “DSO compounds” and “ODSOcompounds,” and each form may be used interchangeably. In certaininstances, a singular ODSO compound may also be referenced.

In the process herein, an effective amount of one or more ODSO compoundsare used in the synthesis of beta zeolites. In certain embodiments aneffective amount can be based on an amount that attains a desired pHrange. In certain embodiments an effective amount can be approximatelyequivalent to a reduction in the amount of water that is used in thehomogeneous aqueous mixture compared to synthesis without ODSO. Incertain embodiments an effective amount can be based on a ratio of ODSOto alkali metal. In certain embodiments a ratio of ODSO to alkali metalrepresents the amount of ODSO relative to the amount of the selectedalkali metal on a mass/mass basis or a molar/molar basis. For example,if sodium is used the ratio is expressed as ODSO/Na on a mass/mass basisor a molar/molar basis. In certain embodiments, the effective amount ofODSO is that which results in a pH level of greater than or equal toabout 9, for example in the range of about 9-14, 9-13, 10-14, 10-13,11-14 or 11-13 in the homogeneous aqueous mixture. In certainembodiments, the effective amount of ODSO can be relative to thequantity of basic groups in the homogeneous aqueous mixture, such asOH—, to attain a desired pH range, with basic group contributions fromthe alkali metal source or in certain embodiments from the alkali metalsource and from a structure directing agent containing basic groups;such a ratio can be expressed on a molar basis or on a mass basis. Incertain embodiments, the effective amount of ODSO is that which resultsin a product that is at least about 0.1 mass % zeolite beta. In certainembodiments in which the ratios of materials in the homogeneous aqueousmixture are suitable for production of zeolite beta in the absence ofODSO, the effective amount of ODSO is less than that which produces 100mass % mordenite zeolite. In certain embodiments in which the ratios ofmaterials in the homogeneous aqueous mixture are suitable for productionof zeolite beta in the absence of ODSO, mordenite zeolite is produced asa co-product, and the effective amount of ODSO is greater than thatwhich produces 100 mass % mordenite zeolite, and less than the amount ofODSO that produces amorphous materials and/or other crystallinematerials.

In certain embodiments, the ODSO compounds used as a component hereinfor zeolite synthesis are obtained from controlled catalytic oxidationof disulfide oils from mercaptan oxidation processes. The effluents fromcontrolled catalytic oxidation of disulfide oils from mercaptanoxidation processes includes ODSO compounds and in certain embodimentsDSO compounds that were unconverted in the oxidation process. In certainembodiments this effluent contains water-soluble compounds andwater-insoluble compounds. The effluent contains at least one ODSOcompound, or a mixture of two or more ODSO compounds, selected from thegroup consisting of compounds having the general formula (R—SO—S—R′),(R—SOO—S—R′), (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH),(R—SO—SO—OR′), (R—SOO—SO—OR′), (R—SO—SOO—OR′) and (R—SOO—SOO—OR′). Incertain embodiments, in the above formulae R and R′ are can be the sameor different C1-C10 alkyl or C6-C10 aryl. It will be understood thatsince the source of the DSO is a refinery feedstream, the R substituentsvary, e.g., methyl and ethyl subgroups, and the number of sulfur atoms,S, in the as-received feedstream to oxidation can extend to 3, forexample, trisulfide compounds.

In certain embodiments the water-soluble compounds and water-insolublecompounds are separated from one another, and a component used hereinfor zeolite synthesis comprises all or a portion of the water-solublecompounds separated from the total effluents from oxidation of disulfideoils from mercaptan oxidation processes. For example, the differentphases can be separated by decantation or partitioning with a separatingfunnel, separation drum, by decantation, or any other known apparatus orprocess for separating two immiscible phases from one another. Incertain embodiments, the water-soluble and water-insoluble componentscan be separated by distillation as they have different boiling pointranges. It is understood that there will be crossover of thewater-soluble and water-insoluble components in each fraction due tosolubility of components, typically in the ppmw range (for instance,about 1-10,000, 1-1,000, 1-500 or 1-200 ppmw). In certain embodiments,contaminants from each phase can be removed, for example by stripping oradsorption.

In certain embodiments a component used herein for zeolite synthesiscomprises, consists of or consists essentially of at least onewater-soluble ODSO compound having 3 or more oxygen atoms that isselected from the group consisting of compounds having the generalformula (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SOO—SO—OH), (R—SO—SO—OR′), (R—SOO—SO—OR′), (R—SO—SOO—OR′) and(R—SOO—SOO—OR′). In certain embodiments a component used herein forzeolite synthesis comprises, consists of or consists essentially of amixture or two or more water-soluble ODSO compounds having 3 or moreoxygen atoms, that is selected from the group consisting of compoundshaving the general formula (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH),(R—SOO—SOO—OH), (R—SOO—SO—OH), (R—SO—SO—OR′), (R—SOO—SO—OR′),(R—SO—SOO—OR′) and (R—SOO—SOO—OR′). In certain embodiments a componentused herein for zeolite synthesis comprises, consists of or consistsessentially of ODSO compounds selected from the group consisting of(R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SO—SO—OH), (R—SOO—SO—OH), and mixtures thereof. In certainembodiments, in the above formulae R and R′ can be the same or differentC1-C10 alkyl or C6-C10 aryl. In certain embodiments, the R and R′ aremethyl and/or ethyl groups. In certain embodiments, the ODSO compound(s)used herein as a component for zeolite synthesis have 1 to 20 carbonatoms.

In certain embodiments, a component used herein for zeolite synthesiscomprises, consists of or consists essentially of ODSO compounds havingan average density greater than about 1.0 g/cc. In certain embodiments,a component used herein for zeolite synthesis comprises, consists of orconsists essentially of ODSO compounds having an average boiling pointgreater than about 80° C. In certain embodiments, a component usedherein for zeolite synthesis comprises, consists of or consistsessentially of ODSO compounds having a dielectric constant that is lessthan or equal to 100 at 0° C.

Table 1 includes examples of polar water-soluble ODSO compounds thatcontain 3 or more oxygen atoms. In certain embodiments the identifiedODSO compounds are obtained from a water-soluble fraction of theeffluents from oxidation of DSO obtained from MEROX by-products. TheODSO compounds that contain 3 or more oxygen atoms are water-solubleover effectively all concentrations, for instance, with some minoramount of acceptable tolerance for carry over components from theeffluent stream and in the water insoluble fraction with 2 oxygen atomsof no more than about 1, 3 or 5 mass percent.

In certain embodiments the ODSO compounds used as a component forzeolite synthesis comprise all or a portion of the ODSO compoundscontained in an oxidation effluent stream that is obtained by controlledcatalytic oxidation of MEROX process by-products, DSO compounds, asdisclosed in U.S. Pat. Nos. 10,807,947 and 10,781,168 and asincorporated herein by reference above.

In some embodiments, the ODSO compounds used as a component for zeolitesynthesis are derived from oxidized DSO compounds present in an effluentrefinery hydrocarbon stream recovered following the catalytic oxidationof mercaptans present in the hydrocarbon stream. In some embodiments,the DSO compounds are oxidized in the presence of a catalyst.

As noted above, the designation “MEROX” originates from the function ofthe process itself, that is, the conversion of mercaptans by oxidation.The MEROX process in all of its applications is based on the ability ofan organometallic catalyst in a basic environment, such as a caustic, toaccelerate the oxidation of mercaptans to disulfides at near ambienttemperatures and pressures. The overall reaction can be expressed asfollows:RSH+¼O₂→½RSSR+½H₂O  (1)where R is a hydrocarbon chain that may be straight, branched, orcyclic, and the chains can be saturated or unsaturated. In mostpetroleum fractions, there will be a mixture of mercaptans so that the Rcan have 1, 2, 3 and up to 10 or more carbon atoms in the chain. Thisvariable chain length is indicated by R and R′ in the reaction. Thereaction is then written:2R′SH+2RSH+O₂→2R′SSR+2H₂O  (2)

This reaction occurs spontaneously whenever any sour mercaptan-bearingdistillate is exposed to atmospheric oxygen, but proceeds at a very slowrate. In addition, the catalyzed reaction (1) set forth above requiresthe presence of an alkali caustic solution, such as aqueous sodiumhydroxide. The mercaptan oxidation proceeds at an economically practicalrate at moderate refinery downstream temperatures.

The MEROX process can be conducted on both liquid streams and oncombined gaseous and liquid streams. In the case of liquid streams, themercaptans are converted directly to disulfides which remain in theproduct so that there is no reduction in total sulfur content of theeffluent stream. The MEROX process typically utilizes a fixed bedreactor system for liquid streams and is normally employed with chargestocks having end points above 135° C.-150° C. Mercaptans are convertedto disulfides in the fixed bed reactor system over a catalyst, forexample, an activated charcoal impregnated with the MEROX reagent, andwetted with caustic solution. Air is injected into the hydrocarbonfeedstream ahead of the reactor and in passing through thecatalyst-impregnated bed, the mercaptans in the feed are oxidized todisulfides. The disulfides are substantially insoluble in the causticand remain in the hydrocarbon phase. Post treatment is required toremove undesirable by-products resulting from known side reactions suchas the neutralization of H₂S, the oxidation of phenolic compounds,entrained caustic, and others.

The vapor pressures of disulfides are relatively low compared to thoseof mercaptans, so that their presence is much less objectionable fromthe standpoint of odor; however, they are not environmentally acceptabledue to their sulfur content and their disposal can be problematical.

In the case of mixed gas and liquid streams, extraction is applied toboth phases of the hydrocarbon streams. The degree of completeness ofthe mercaptan extraction depends upon the solubility of the mercaptansin the alkaline solution, which is a function of the molecular weight ofthe individual mercaptans, the extent of the branching of the mercaptanmolecules, the concentration of the caustic soda and the temperature ofthe system. Thereafter, the resulting DSO compounds are separated andthe caustic solution is regenerated by oxidation with air in thepresence of the catalyst and reused.

Referring to the attached drawings, FIG. 1 is a simplified schematic ofa generalized version of a conventional MEROX process employingliquid-liquid extraction for removing sulfur compounds. A MEROX unit1010, is provided for treating a mercaptan containing hydrocarbon stream1001. In some embodiments, the mercaptan containing hydrocarbon stream1001 is LPG, propane, butane, light naphtha, kerosene, jet fuel, or amixture thereof. The process generally includes the steps of:introducing the hydrocarbon stream 1001 with a homogeneous catalyst intoan extraction vessel 1005 containing a caustic solution 1002, in someembodiments, the catalyst is a homogeneous cobalt-based catalyst;passing the hydrocarbon catalyst stream in counter-current flow throughthe extraction section of the extraction 1005 vessel in which theextraction section includes one or more liquid-liquid contactingextraction decks or trays (not shown) for the catalyzed reaction withthe circulating caustic solution to convert the mercaptans towater-soluble alkali metal alkane thiolate compounds; withdrawing ahydrocarbon product stream 1003 that is free or substantially free ofmercaptans from the extraction vessel 1005, for instance, having no morethan about 1000, 100, 10 or 1 ppmw mercaptans; recovering a combinedspent caustic and alkali metal alkane thiolate stream 1004 from theextraction vessel 1005; subjecting the spent caustic and alkali metalalkane thiolate stream 1004 to catalyzed wet air oxidation in a reactor1020 into which is introduced catalyst 1005 and air 1006 to provide theregenerated spent caustic 1008 and convert the alkali metal alkanethiolate compounds to disulfide oils; and recovering a by-product stream1007 of DSO compounds and a minor proportion of other sulfides such asmono-sulfides and tri-sulfides. The effluents of the wet air oxidationstep in the MEROX process can comprise a minor proportion of sulfidesand a major proportion of disulfide oils. As is known to those skilledin the art, the composition of this effluent stream depends on theeffectiveness of the MEROX process, and sulfides are assumed to becarried-over material. A variety of catalysts have been developed forthe commercial practice of the process. The efficiency of the MEROXprocess is also a function of the amount of H₂S present in the stream.It is a common refinery practice to install a prewashing step for H₂Sremoval.

An enhanced MEROX process (“E-MEROX”) is a modified MEROX process wherean additional step is added, in which DSO compounds are oxidized with anoxidant in the presence of a catalyst to produce a mixture of ODSOcompounds. The by-product DSO compounds from the mercaptan oxidationprocess are oxidized, in some embodiments in the presence of a catalyst,and constitute an abundant source of ODSO compounds that are sulfoxides,sulfonates, sulfinates, sulfones and their corresponding di-sulfurmixtures. The disulfide oils having the general formula RSSR′ (wherein Rand R′ can be the same or different and can have 1, 2, 3 and up to 10 ormore carbon atoms) can be oxidized without a catalyst or in the presenceof one or more catalysts to produce a mixture of ODSO compounds. Theoxidant can be a liquid peroxide selected from the group consisting ofalkyl hydroperoxides, aryl hydroperoxides, dialkyl peroxides, diarylperoxides, peresters and hydrogen peroxide. The oxidant can also be agas, including air, oxygen, ozone and oxides of nitrogen. If a catalystis used in the oxidation of the disulfide oils having the generalformula RSSR′ to produce the ODSO compounds, it can be a heterogeneousor homogeneous oxidation catalyst. The oxidation catalyst can beselected from one or more heterogeneous or homogeneous catalystcomprising metals from the IUPAC Group 4-12 of the Periodic Table,including Ti, V, Mn, Co, Fe, Cr, Cu, Zn, W and Mo. The catalyst can be ahomogeneous water-soluble compound that is a transition metal containingan active species selected from the group consisting of Mo (VI), W (VI),V (V), Ti (IV), and their combination. In certain embodiments, suitablehomogeneous catalysts include molybdenum naphthenate, sodium tungstate,molybdenum hexacarbonyl, tungsten hexacarbonyl, sodium tungstate andvanadium pentoxide. An exemplary catalyst for the controlled catalyticoxidation of MEROX process by-products DSO is sodium tungstate,Na₂WO₄·2H₂O. In certain embodiments, suitable heterogeneous catalystsinclude Ti, V, Mn, Co, Fe, Cr, W, Mo, and combinations thereof depositedon a support such as alumina, silica-alumina, silica, natural zeolites,synthetic zeolites, and combinations comprising one or more of the abovesupports.

The oxidation of DSO typically is carried out in an oxidation vesselselected from one or more of a fixed-bed reactor, an ebullated bedreactor, a slurry bed reactor, a moving bed reactor, a continuousstirred tank reactor, and a tubular reactor. The ODSO compounds producedin the E-MEROX process generally comprise two phases: a water-solublephase and water-insoluble phase, and can be separated into the aqueousphase containing water-soluble ODSO compounds and a non-aqueous phasecontaining water-insoluble ODSO compounds. The E-MEROX process can betuned depending on the desired ratio of water-soluble to water-insolublecompounds presented in the product ODSO mixture. Partial oxidation ofDSO compounds results in a higher relative amount of water-insolubleODSO compounds present in the ODSO product and a near or almost completeoxidation of DSO compounds results in a higher relative amount ofwater-soluble ODSO present in the ODSO product. Details of the ODSOcompositions are discussed in the U.S. Pat. No. 10,781,168, which isincorporated herein by reference above.

FIG. 2 is a simplified schematic of an E-MEROX process that includesE-MEROX unit 1030. The MEROX unit 1010 unit operates similarly as inFIG. 1 , with similar references numbers representing similarunits/feeds. In FIG. 2 , the effluent stream 1007 from the generalizedMEROX unit of FIG. 1 is treated. It will be understood that theprocessing of the mercaptan containing hydrocarbon stream of FIG. 1 isillustrative only and that separate streams of the products, andcombined or separate streams of other mixed and longer chain productscan be the subject of the process for the recovery and oxidation of DSOto produce ODSO compounds, that is the E-MEROX process. In order topractice the E-MEROX process, apparatus are added to recover theby-product DSO compounds from the MEROX process. In addition, a suitablereactor 1035 add into which the DSO compounds are introduced in thepresence of a catalyst 1032 and an oxidant 1034 and subjecting the DSOcompounds to a catalytic oxidation step to produce the mixed stream 1036of water and ODSO compounds. A separation vessel 1040 is provided toseparate the by-product 1044 from the ODSO compounds 1042.

The oxidation to produce OSDO can be carried out in a suitable oxidationreaction vessel operating at a pressure in the range from about 1-30,1-10 or 1-3 bars. The oxidation to produce OSDO can be carried out at atemperature in the range from about 20-300, 20-150, 20-90, 45-300,15-150 or 45-90° C. The molar feed ratio of oxidizingagent-to-mono-sulfur can be in the range of from about 1:1 to 100:1, 1:1to 30:1 or 1:1 to 4:1. The residence time in the reaction vessel can bein the range of from about 5-180, 5-90, 5-30, 15-180, 15-90 or 5-30minutes. In certain embodiments, oxidation of DSO is carried out in anenvironment without added water as a reagent. The by-products stream1044 generally comprises wastewater when hydrogen peroxide is used asthe oxidant. Alternatively, when other organic peroxides are used as theoxidant, the by-products stream 1044 generally comprises the alcohol ofthe peroxide used. For example, if butyl peroxide is used as theoxidant, the by-product alcohol 1044 is butanol.

In certain embodiments water-soluble ODSO compounds are passed to afractionation zone (not shown) for recovery following their separationfrom the wastewater fraction. The fractionation zone can include adistillation unit. In certain embodiments, the distillation unit can bea flash distillation unit with no theoretical plates in order to obtaindistillation cuts with larger overlaps with each other or,alternatively, on other embodiments, the distillation unit can be aflash distillation unit with at least 15 theoretical plates in order tohave effective separation between cuts. In certain embodiments, thedistillation unit can operate at atmospheric pressure and at atemperature in the range of from 100° C. to 225° C. In otherembodiments, the fractionation can be carried out continuously undervacuum conditions. In those embodiments, fractionation occurs at reducedpressures and at their respective boiling temperatures. For example, at350 mbar and 10 mbar, the temperature ranges are from 80° C. to 194° C.and 11° C. to 98° C., respectively. Following fractionation, thewastewater is sent to the wastewater pool (not shown) for conventionaltreatment prior to its disposal. The wastewater by-product fraction cancontain a small amount of water-insoluble ODSO compounds, for example,in the range of from 1 ppmw to 10,000 ppmw. The wastewater by-productfraction can contain a small amount of water-soluble ODSO compounds, forexample, in the range of from 1 ppmw to 50,000 ppmw, or 100 ppmw to50,000 ppmw. In embodiments where alcohol is the by-product alcohol, thealcohol can be recovered and sold as a commodity product or added tofuels like gasoline. The alcohol by-product fraction can contain a smallamount of water-insoluble ODSO compounds, for example, in the range offrom 1 ppmw to 10,000 ppmw. The alcohol by-product fraction can containa small amount of water-soluble ODSO compounds, for example, in therange of from 100 ppmw to 50,000 ppmw.

Examples

The below example and data are exemplary. It is to be understood thatother ratios and types of aluminum sources, silica sources, bases andstructure directing agents can be used as compared to the example.

Reference Example: The ODSO mixture used in the Example below wasproduced as disclosed in U.S. Pat. No. 10,781,168, incorporated byreference above, and in particular the fraction referred to therein asComposition 2. Catalytic oxidation a hydrocarbon refinery feedstockhaving 98 mass percent of C1 and C2 disulfide oils was carried out. Theoxidation of the DSO compounds was performed in batch mode under refluxat atmospheric pressure, that is, approximately 1.01 bar. The hydrogenperoxide oxidant was added at room temperature, that is, approximately23° C. and produced an exothermic reaction. The molar ratio ofoxidant-to-DSO compounds (calculated based upon mono-sulfur content) was2.9. After the addition of the oxidant was complete, the reaction vesseltemperature was set to reflux at 80° C. for approximately one hour afterwhich the water soluble ODSO was produced (referred to as Composition 2herein and in U.S. Pat. No. 10,781,168) and isolated after the removalof water. The catalyst used in the oxidation of the DSO compounds wassodium tungstate. The Composition 2, referred to herein as “the selectedwater soluble ODSO fraction,” was used. FIG. 3A is the experimental1H-NMR spectrum of the polar, water soluble ODSO mixture that is theselected water soluble ODSO fraction in the example herein. FIG. 3B isthe experimental ¹³C-DEPT-135-NMR spectrum of the polar, water solubleODSO mixture that is the selected water soluble ODSO fraction in theexample herein. The selected water soluble ODSO fraction was mixed witha CD₃OD solvent and the spectrum was taken at 25° C. Methyl carbons havea positive intensity while methylene carbons exhibit a negativeintensity. The peaks in the 48-50 ppm region belong to carbon signals ofthe CD₃OD solvent.

When comparing the experimental ¹³C-DEPT-135-NMR spectrum of FIG. 3B forthe selected water soluble ODSO fraction with a saved database ofpredicted spectra, it was found that a combination of the predictedalkyl-sulfoxidesulfonate (R—SO—SOO—OH), alkyl-sulfonesulfonate(R—SOO—SOO—OH), alkyl-sulfoxidesulfinate (R—SO—SO—OH) andalkyl-sulfonesulfinate (R—SOO—SO—OH) most closely corresponded to theexperimental spectrum. This suggests that alkyl-sulfoxidesulfonate(R—SO—SOO—OH), alkyl-sulfonesulfonate (R—SOO—SOO—OH),alkyl-sulfoxidesulfinate (R—SO—SO—OH) and alkyl-sulfonesulfinate(R—SOO—SO—OH) are major compounds in the selected water soluble ODSOfraction. It is clear from the NMR spectra shown in FIGS. 3A and 3B thatthe selected water soluble ODSO fraction comprises a mixture of ODSOcompounds that form the ODSO composition used in the present examples.

Comparative Example: In a comparative example, zeolite beta wassynthesized using conventional precursors and water as solvent, forinstance with a sol-gel SAR of about 30. Aluminum nitrate nonahydrate(0.6955 g) was weighed into a polytetrafluoroethylene (PTFE) liner (45ml). Thereafter, 0.8144 g of a 50 wt. % sodium hydroxide solution and5.0878 g tetraethylammonium hydroxide (TEAOH, 40 wt. %) were added andthe mixture stirred until the aluminum source dissolved. Next, distilledwater (6.2386 g) was added and the mixture was kept under stirring. Thesilica source, (4.1737 g, 40 wt. %), was added and the mixture stirreduntil homogeneous. The PTFE liner was positioned within an autoclave andtransferred to an oven and heated to a temperature of 140° C. whilstrotating the autoclave. The autoclave was kept at isothermal conditionsfor 6 days. Thereafter, the product was filtered and washed withdistilled water before drying at 110° C. The dry mass was 1.1530 g. Theinorganic content determined by thermogravimetric (TGA) analysis was79.1%, which corresponds to a zeolite yield of 0.9119 g. The as-madesample was calcined at 550° C. (1° C./min ramp rate) for 8 hours torealize the porous zeolite.

Example: ODSO as described in the Reference Example was included in thehomogeneous aqueous mixture to synthesize zeolite beta. As in theComparative Example, precursors were used with a sol-gel SAR of about30. Aluminum nitrate nonahydrate (0.6943 g) was weighed into a PTFEliner (45 ml). Thereafter, 0.8135 g of a 50 wt. % sodium hydroxidesolution and 5.1063 g tetraethylammonium hydroxide (TEAOH, 40 wt. %)were added and the mixture stirred until the aluminum source dissolved.Next, distilled water (5.9178 g) and ODSO (0.31111 g) were added and themixture was kept under stirring. Finally, the silica source, (4.1695 g,40 wt. %), was added and the mixture stirred until homogeneous. The PTFEliner was positioned within an autoclave and transferred to an oven andheated to a temperature of 140° C. whilst rotating the autoclave. Theautoclave was kept at isothermal conditions for 6 days. Thereafter, theproduct was filtered and washed with distilled water before drying at110° C. The dry mass was 1.3452 g. The inorganic content determined bythermogravimetric (TGA) analysis was 77.1%, which corresponds to azeolite yield of 1.0371 g, and is approximately a 14% increase in yieldrelative to the comparative example. The as-made sample was calcined at550° C. (1° C./min ramp rate) for 8 hours to realize the porous zeolite.

FIG. 4 shows X-ray diffraction patterns of the as-made zeolites (priorto calcination) where each pattern is offset on the y-axis by anequivalent amount for clarity, which is an effective way to comparepatterns relative to one another. Both patterns clearly show presence ofzeolite beta. In the upper pattern shown in dashed lines, representingsynthesis including ODSO at ratio of ODSO/Na (w/w) of 1.33, peaks areshown indicative zeolite beta. In the lower pattern shown in a solidline, representing the comparative example without ODSO, the pattern isalso indicative of zeolite beta.

Table 2 identifies the structure of the product as a function of theODSO content. Under approximately equivalent ratios ofprecursors/reagents, and under approximately equivalent synthesisprocess conditions, with ODSO/Na ratios that are higher than those forzeolite beta only (for instance as in the example herein), zeolitemordenite is produced (wherein the ODSO/Na ratios are about 2.7, 4.0,5.3 or 6.7 in the examples disclosed in commonly owned U.S. applicationSer. No. 17/720,012 filed on Apr. 13, 2022, entitled “Method ForManufacture Of Zeolite Mordenite In The Presence Of ODSO” which isincorporated by reference herein in its entirety. With a furtherincrease in ODSO/Na ratios, co-crystallized zeolite beta and zeolitemordenite is produced (wherein the ODSO/Na ratios are about 8 in theexamples disclosed in commonly owned U.S. application Ser. No.17/719,848 filed on Apr. 13, 2022, entitled “Method for Manufacture ofCo-Crystallized Zeolite Beta and Zeolite Mordenite in the Presence ofODSO” which is incorporated by reference herein in its entirety. Underapproximately equivalent ratios of precursors/reagents, and underapproximately equivalent synthesis process conditions, with ODSO/Naratios that are higher than those for co-crystallized zeolite beta andzeolite mordenite (for instance at or above about 9.3), amorphousmaterial and in some instances other unidentified crystalline materialis produced. In certain embodiments of the present process for producingzeolite beta, an ODSO/Na mass ratio can be in the range of about0.1-1.8, 0.1-1.5, 0.5-1.8 or 0.5-1.5. In embodiments in which zeolitebeta is co-crystallized with zeolite mordenite, there is at least 0.1mass % zeolite beta, and accordingly in certain embodiments an ODSO/Namass ratio can be in the range of about 7.5-8.5, 7.5-8.2, 7.7-8.5,7.7-8.2 or 7.9-8.1. In certain embodiments, the effective amount of ODSOis expressed as ODSO/Na mass ratio ranges, which is calculated from abaseline compositional ratio of 30 SiO₂:1 Al₂O₃:5.5 Na₂O:15 TEA:750 H₂Oon a molar basis. In the Example, approximately equivalent conditions,time and ratios were used, except that an approximately equivalent massof water was replaced with ODSO and hence the ODSO-enhancedcompositional ratio is approximately equivalent to the baselinecompositional ratio for the Comparative Example.

It is also noted that the amount of sodium would be adjusted based onthe anions in other sol-gel components. For instance, in the examplesherein a portion of the sodium cations in the quantity of Na₂Ocounterbalances nitrate anions that form the aluminum source (aluminumnitrate nonahydrate), for instance, 3 of the 5.5 moles of Na₂O that arepresent in the compositional ratio counter the anions; with an aluminumsource that does not include such anions or contains less anions, therequired amount of sodium cations is reduced (for instance, if no anionsare present in the aluminum source, an equivalent compositional ratiowould include 2.5 moles of Na₂O).

FIG. 5 shows a thermogravimetric mass loss profile of the zeolite betaaccording to the example herein and the comparative example. Normalizedzeolite yield is based on the dry mass of the as-made zeolite multipliedby the inorganic content determined from thermogravimetric analysis. AnODSO/Na ratio=0 is a water-only synthesis in the absence of ODSO. FIG. 5and Table 2, demonstrate the increase in normalized yield.

As used herein, “approximately equivalent” as concerning the amount ofODSO that replaces water, the cumulative amount of ODSO and water, thecomponent molar or mass ratios, and/or the hydrolysis conditions andtime, is within a margin of less than or equal to plus or minus 1, 2, 5or 10% of the compared value.

It is to be understood that like numerals in the drawings represent likeelements through the several figures, and that not all components and/orsteps described and illustrated with reference to the figures arerequired for all embodiments or arrangements. Further, the terminologyused herein is for the purpose of describing particular embodiments onlyand is not intended to be limiting of the invention. As used herein, thesingular forms “a”, “an” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise. It willbe further understood that the terms ““including,” “comprising,” or“having,” “containing,” “involving,” and variations thereof herein, whenused in this specification, specify the presence of stated features,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,integers, steps, operations, elements, components, and/or groupsthereof.

It should be noted that use of ordinal terms such as “first,” “second,”“third,” etc., in the claims to modify a claim element does not byitself connote any priority, precedence, or order of one claim elementover another or the temporal order in which acts of a method areperformed, but are used merely as labels to distinguish one claimelement having a certain name from another element having a same name(but for use of the ordinal term) to distinguish the claim elements.

Notably, the figures and examples above are not meant to limit the scopeof the present disclosure to a single implementation, as otherimplementations are possible by way of interchange of some or all thedescribed or illustrated elements. Moreover, where certain elements ofthe present disclosure can be partially or fully implemented using knowncomponents, only those portions of such known components that arenecessary for an understanding of the present disclosure are described,and detailed descriptions of other portions of such known components areomitted so as not to obscure the disclosure. In the presentspecification, an implementation showing a singular component should notnecessarily be limited to other implementations including a plurality ofthe same component, and vice-versa, unless explicitly stated otherwiseherein. Moreover, applicants do not intend for any term in thespecification or claims to be ascribed an uncommon or special meaningunless explicitly set forth as such. Further, the present disclosureencompasses present and future known equivalents to the known componentsreferred to herein by way of illustration.

The foregoing description of the specific implementations will so fullyreveal the general nature of the disclosure that others can, by applyingknowledge within the skill of the relevant art(s), readily modify and/oradapt for various applications such specific implementations, withoutundue experimentation, without departing from the general concept of thepresent disclosure. Such adaptations and modifications are thereforeintended to be within the meaning and range of equivalents of thedisclosed implementations, based on the teaching and guidance presentedherein. It is to be understood that the phraseology or terminologyherein is for the purpose of description and not of limitation, suchthat the terminology or phraseology of the present specification is tobe interpreted by the skilled artisan in light of the teachings andguidance presented herein, in combination with the knowledge of oneskilled in the relevant art(s). It is to be understood that dimensionsdiscussed or shown are drawings accordingly to one example and otherdimensions can be used without departing from the disclosure.

The subject matter described above is provided by way of illustrationonly and should not be construed as limiting. Various modifications andchanges can be made to the subject matter described herein withoutfollowing the example embodiments and applications illustrated anddescribed, and without departing from the true spirit and scope of theinvention encompassed by the present disclosure, which is defined by theset of recitations in the following claims and by structures andfunctions or steps which are equivalent to these recitations.

TABLE 1 ODSO Name Formula Structure Examples Dialkyl-sulfonesulfoxide Or1,2-alkyl-alkyl-disulfane 1,1,2-trioxide (R—SOO—SO—R')

1,2-Dimethyldisulfane 1,1,2-trioxide Dialkyl-disulfone Or 1,2alkyl-alkyl-disulfane 1,1,2,2-tetraoxide (R—SOO—SOO-—R')

1,2-Dimethyldisulfane 1,1,2,2- tetraoxide Alkyl-sulfoxidesulfonate(R—SO—SOO—OH)

Methylsulfanesulfonic acid oxide Alkyl-sulfonesulfonate (R—SOO—SOO—OH)

1-Hydroxy-2-methyldisulfane 1,1,2,2- tetraoxide Alkyl-sulfoxidesulfinate(R—SO—SO—OH)

1-Hydroxy-2-methyldisulfane 1,2- dioxide Alkyl-sulfonesulfinate(R—SOO—SO—OH)

Methylsulfanesulfinic acid dioxide R and R' can be the same or differentC1-C10 alkyl or C6-C10 aryl.

TABLE 2 ODSO/Na Water Substitu- Normalized Ratio (w/w) tion (w %)*Product Structure Yield 0 0 *BEA zeolite 1.00 1.32 5 1.14 2.66 10 MORzeolite 1.15 3.99 15 1.23 5.27 20 1.40 6.67 25 1.53 7.97 30 *BEA/MORzeolite 1.74 9.30 35 amorphous 1.94 10.66 40 1.93 15.94 60 amorphousplus 1.76 21.35 80 unknown crystalline 1.62 26.46 100 phase 1.71 *Notethat the water substitution refers to the replacement of the utilitywater that is added to form the homogeneous aqueous mixture, andexcludes water added from certain precursors/reagents.

What is claimed is:
 1. A method for the preparation of beta zeolitecomprising: forming a homogeneous aqueous mixture of water, a silicasource, an aluminum source, an alkali metal source, an optionalstructure directing agent, and water-soluble oxidized disulfide oil(ODSO); and heating the homogeneous aqueous mixture under conditions andfor a time effective for hydrolysis and to form a crystalline zeolite asprecipitate suspended in a supernatant, wherein the precipitatecomprises beta zeolite.
 2. The method of claim 1, wherein theprecipitate is received and calcined at a suitable temperature,temperature ramp rate and for a suitable period of time to realizeporous beta zeolite.
 3. The method of claim 1, wherein a cumulativeamount of ODSO and water is approximately equivalent to an amount ofwater that is effective to produce beta zeolite in the absence of ODSO;the cumulative amount of ODSO and water, an amount of the silica source,an amount of the aluminum source, an amount of the alkali metal source,and an amount of the optional structure directing agent are provided atan ODSO-enhanced compositional ratio; the ODSO-enhanced compositionalratio is approximately equivalent to a baseline compositional ratio ofwater, silica source, aluminum source, alkali metal source and optionalstructure directing agent, the baseline compositional ratio beingeffective to produce beta zeolite in the absence of ODSO; and theconditions and time of heating are approximately equivalent to thosethat are effective to produce beta zeolite in the absence of ODSO. 4.The method as in claim 3, wherein the beta zeolite comprises at leastabout 0.1 mass % of the precipitate, and wherein the amount of ODSO isgreater than 0.1 mass % ODSO relative to the total mass of thehomogeneous aqueous mixture, and is less than an amount of ODSO thatproduces only zeolite mordenite; or wherein the amount of ODSO isgreater than an amount of ODSO that produces only zeolite mordenite, andless than an amount of ODSO that produces only amorphous material and/orother crystalline material.
 5. The method as in claim 3, wherein thealkali metal source is sodium and the mass ratio of ODSO to sodium is inthe range of about 0.1 to 1.8 or 7.5-8.5.
 6. The method as in claim 1,wherein the ODSO is derived from oxidation of disulfide oil compoundspresent in an effluent refinery hydrocarbon stream recovered followingcatalytic oxidation of mercaptans present in a mercaptan-containinghydrocarbon stream.
 7. The method as in claim 1, wherein the ODSOcompounds have 3 or more oxygen atoms and include one or more compoundsselected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (R—SO—SO—OR′),(R—SOO—SO—OR′), (R—SO—SOO—OR′) and (R—SOO—SOO—OR′), wherein R and R′ canbe the same or different C1-C10 alkyl or C6-C10 aryl.
 8. The method asin claim 1, wherein the ODSO compounds have 3 or more oxygen atoms andinclude two or more compounds selected from the group consisting of(R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH),(R—SOO—SO—OH), (R—SO—SO—OR′), (R—SOO—SO—OR′), (R—SO—SOO—OR′) and(R—SOO—SOO—OR′), wherein R and R′ can be the same or different C1-C10alkyl or C6-C10 aryl.
 9. The method as in claim 1, wherein the ODSOcompounds have 3 or more oxygen atoms and include one or more compoundsselected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′),(R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SO—SO—OH), (R—SOO—SO—OH), wherein Rand R′ can be the same or different C1-C10 alkyl or C6-C10 aryl.
 10. Themethod as in claim 1, wherein a silica-to-alumina ratio (SAR) in thezeolite is between about 10 and
 10000. 11. The method as in claim 1,wherein the aluminum source is selected from the group consisting ofaluminates, alumina, other zeolites, aluminum colloids, boehmites,pseudo-boehmites, aluminum hydroxides, aluminum salts, aluminumalkoxides, aluminum wire and alumina gels.
 12. The method as in claim 1,wherein the silica source is selected from the group consisting ofsodium silicate (water glass), rice husk, fumed silica, precipitatedsilica, colloidal silica, silica gels, zeolites, dealuminated zeolites,silicon hydroxides and silicon alkoxides.
 13. The method as in claim 1,wherein the structure directing agent is used to stabilize the zeolitestructure.
 14. The method as in claim 13, wherein the structuredirecting agent is selected from the group consisting of quaternaryammonium ions, trialkylamines, dialkylamines, monoalkylamines, cyclicamines, alkylethanol amines, cyclic diamines, alkyl diamines, alkylpolyamines, alcohols, ketones, morpholine, and glycerol.
 15. The methodas in claim 13, wherein the structure directing agent comprises a cationselected from the group consisting of tetramethylammonium,tetraethylammonium, tetrapropylammonium, tetrabutylammonium, andcetyltrimethylammonium, paired with an anion selected from the groupconsisting of hydroxide, bromide and iodide.
 16. The method as in claim13, wherein the structure directing agent is selected from the groupconsisting of 4,4′trimethylene bis(N-methyl N-benzyl-piperidinium)hydroxide, 1,2-diazabicyclo 2,2,2, octane, dialkylbenzyl ammoniumhydroxide, dimethyldiisopropylammonium hydroxide,N,N-dimethyl-2,6-cis-dimethylpiperdinium hydroxide,N-ethyl-N,N-dimethylcyclohexanaminium hydroxide,N,N,N-trimethylcyclohexanaminium hydroxide,N-isopropyl-N-methyl-pyrrolidinium, N-isobutyl-N-methyl-pyrrolidinium(iButOH), and N-isopentyl-N-methyl-pyrrolidinium (iPenOH).
 17. Themethod as in claim 1, wherein crystallization occurs in the absence of aseed.
 18. The method as in claim 1, wherein crystallization occurs inthe presence of a seed.
 19. The method as in claim 1, wherein the pH ofthe homogeneous aqueous mixture is in the range from about 9-14.
 20. Themethod as in claim 1, wherein the homogeneous aqueous mixture is formedby: (a) providing the silica source; and combining with the silicasource the aluminum oxide source, the alkali metal source, the optionalstructure directing agent and the water-soluble ODSO; wherein thewater-soluble ODSO is added after the aluminum oxide source, the alkalimetal source, and the optional structure directing agent, or wherein thewater-soluble ODSO is first combined with the aluminum oxide source, thealkali metal source and the optional structure directing agent, and thencombined with the silica source; (b) providing the aluminum oxidesource, the alkali metal source and the optional structure directingagent as a first mixture; and combining the first mixture with thesilica source and the water-soluble ODSO; wherein the water-soluble ODSOis added after the silica source; or wherein the water-soluble ODSO isfirst combined with the silica source, and then combined with the firstmixture; (c) combining the water-soluble ODSO with the silica source toform a first mixture; and combining the first mixture with the aluminumoxide source, alkali metal source and the optional structure directingagent; or (d) combining the water-soluble ODSO with the aluminum oxidesource, the alkali metal source and the optional structure directingagent to form a first mixture; and combining the first mixture with thesilica source; and wherein the amount of water for the homogeneousaqueous mixture in (a)-(d) is provided by using utility water, awater-containing silica source, and/or by using an aqueous mixture ofthe aluminum oxide source, the alkali metal source and the optionalstructure directing agent.